New cupriferous trisazo dyestuffs and a proces for their preparation



of the sequestering agent tetrasod-ium salt of ethylene diamine-tetra-acetic acid. This partial demetallisation may also be elfected by simply mixing the sequestering agent with the isolated and dried dicupric compound or by addition of the same agent of the dyebath.

The cupriferous complexes containing one to two atoms of metal per molecule of trisazo compound are especially well suited for dyeing vegetable fibres in shades fastto light and to Washing.

10 The following examples, in which the parts indicated are parts by weight, illustrate the present invention without restricting it.

3,030,352 NEW CUPRIFEROUS TRISAZO DYESTUFFS AND A PROCESS FOR THEIR PREPARATION Marcel Jirou, Sotteville-les-Rouen, and Vasili Urne,

Rotten, France, assignors to Compagnie Francaise des 5 Matieres Color-antes, Paris, France, a company of France No Drawing. Filed Apr. 16, 1959, Ser. No. 806,760 9 Claims. (Cl. 260145) The present invention relates to the copper complexes of the trisazo dyestuffs of the general formula:

I SOaH SOzH in which R represents the residue of an acylaminohydroxynaphthalene-sulphonic acid coupled in the ortho position to the hydroxyl group.

Example 1 109.4 parts of the trisazo dyestufl of the formula OOH: OH

I H! SOaH as the sodium salt are dissolved in 2400 parts of water These complexes can be prepared by dealkylating metat 90 C. This solution is treated with 10 parts of allisation of the dyestutfs of the general formula O-alkyl in which R has the same significance as above, by means sodium bicarbonate. A solution of parts of crystalof compounds of divalent copper. The O-alkyl group is line copper sulphate in 150 parts of water to which 56.5 converted into an hydroxyl group by hydrolysis and theparts of 20% by volume ammonia have been added, is PP becomes attached to the hydroxyl groups in the slowly added. The mixture is heated for 10 hours at OIthO-OIthO' POsition t0 the 320 linkage- 1 90-92 C. and the metallised dyestuif is precipitated by When represents a radical of the formula the addition of sodium chloride, filtered and dried. This dyestufi only contains one atom of metal in its molecule.

Hots NH'acyl It dyes cellulosic fibres a bluish green shade.

Example 2 ()H The dyestufi' employed in Example I is replaced by the excess copper which may possibly be present in the the same weight of the trisazo compound of the formula:

metallisation medium is fixed in its turn. For example, The procedure of Example l is followed, but 50 parts cupriferous compounds containing two atoms of copper of copper sulphate are used instead of 30 parts. A per molecule of dyestuff may be obtained and the solucupric compound 1s obtained which contains two atoms bility of the latter is not thereby reduced. These 2:1 of me al in I s molecule and whlch dyes cellulosic fibres complexes can be used for the preparation of complexes greenlsh blue.

containing only one atom of copper per molecule of trisazo dyestuff, and for this result it is sufiicient to treat the dicupric compounds at C. with a solution Example 3 To the reaction mixture resulting from the metall1sa tion described in Example 2 is added a concentrated soluaoeaaee tion of the tetrasodium salt of ethylenediamine-tetraacetic acid in such quantity that its concentration in the mixture is equal to 1%. After 30 minutes agitation at 8085" C., the dyestufl is isolated by the addition of sodium chloride. The copper complex obtained only contains one atom of metalper molecule of azo dyestutf.

It dyes cellulosic fibres a shade which is a little bluer 15 than that given by the dicupric compound.

Example 4 The copper complex of the trisazo dyestufiof the .7

formula:

is prepared according to the directions in Example 1.

The dyestufi obtained only contains one atom of copper '30 in the molecule and dyes cellulosie fibres green.

We claim: 1. Cupriferous derivatives of trisazo dyestufls of the general formula:

in which R represents a member selected from the group consisting of ,the acetylamiuo-1-hydroxy;monosulpho-2 naphthyl, methoxy carbonylamino-l-hydroxy monosulpho-2-naphthyl, ethoxycarbonylamino-l-hydroxy monosulpho-Z-naphthyl and benzoylamino-l-hydroxy-monosulpho-2-naphthy1 groups, which derivatives contain one to hydroxy-azo grouping resulting from the hydrolysis of the o-methoxyo-hydroXy-azo-grouping.

2. Cupriferous derivatives of trisazo dyestufis of the general formula:

SO H' in which R representsa member selectedfrom the group consisting of the acetylamino-l-hydroXy-monosulpho-2- naphthyl, methoxy carbonylamino-l-hydroxy monosulpho-Z-napht-hyl, ethoxycarbonylamino-l-hydroxy monosulpho-Z-naphthyl and benzoylamino-l-hydroXy-monosulpho-2-naphthyl groups, which derivatives contain one to two atoms of copper per molecule of dyestuif, one of them forming a coordination complex with the o:o-di- OOH; OH NHOOGH solar SOaH SOQH hydroxy-azo grouping resulting from the hydrolysis of the o-methoxy-o'-hydroXy-azo-grouping.

3. The cupriferouscomplex of the trisazo dyestufi of the formula:

in which an atom of divalent copper is attached to the dyestuif by the o.o'-methoxy group.

OCH;

N=NTR 4. The cupriferous complex of the trisazo dyestuff of the formula:

OCHa OH in which at atom of divalent copper is attached to the dyestufi by the o.o'-methoxy group.

5. The cupriferous complex of the trisazo dyestufi of 65 the general formula:

OOHa 0H NHCOCHB two atoms of copper per molecule of dyestuif, one of in which an atom of divalent copperis attached to the them forming a coordination complex with the o:o'-di- 75 dyestuif by the o.o-methoxy group. W

5 6 6. Cupriferous derivatives of the trisazo dyestuif of 8. A process for the preparation of a cupriferous comthe formula: plex containing 1 atom of copper per molecule of dyemfi OH S O H H038 NH 60 303E luHg stuii which comprises effecting a dealkylating coppering 7. A process for the preparation of a cupriferous comof a dyestulf of the general formula:

0 0 Ha O H R represents a member selected from the group consisting of the acetylamino, methoXy-carbonylamino, ethoxy-carbonylamino and benzoylamino groups in the prescontaining two atoms of copper.

plex containing 1 atom of copper per molecule which comprises eifecting a dealkylating coppering of a dye- SO H in which R represents a member selected from the group ence of excess copper, and then efiecting a demetallisaconsisting of the y -ly yp tion of the dicupric derivative by treating said compound naphthyl methoxy carbonylammojl'hydmxy 'monosul with a heated solution of the tetrasodium salt of ethylphO-Z-naphthyl, ethoxycarbony f mono 35 ene-diamine-tetra-acetic acid in an alkaline medium. sulpho-Z-naphthyl and benzoylamino-l-hydroxymonosul- 9 A 1 d 1 8 h h d pho-2-naphthyl groups by reacting said dyestutr in aheat- F Z as 6 m f w m t e ed alkaline medium with a compound of divalent copper metallisatron 111 an alkaline medium 1s effected by means in the ratio f 1 atom f copper l l of d of an aqueous solution of the tetrasodium salt of ethylstuff. 40 enediamine tetra-acetic acid.

References Cited in the file of this patent UNITED STATES PATENTS 1,901,393 Glietenberg Mar. 14, 1933 2,381,599 Krebser et a1 Aug. 7, 1945 2,779,756 Riat Jan. 29, 1957 2,794,798 Durig June 4, 1957 2,817,656 Bissell Dec. 24, 1957 2,834,773 Scalera May 13, 1958 FOREIGN PATENTS 955,715 Germany Ian. 10, 1957 OTHER REFERENCES Taylor, A.: Organic Chelating Agents as Aids to Industry, Chemistry and Industry, No. 41, Oct. 20, 1956, pages 1131-1135. 

1. CUPRIFEROUS DERIVATIVE OF TRISAZO DYESTUFFS OF THE GENERAL FORMULA: 